JPH09114027A - Production of silver halide emulsion, silver halide photographic sensitive material and x-ray image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion having narrow distribution of particle size and a high ratio of planer particles by using such a producing method of a specified silver halide emulsion that consists of process to produce nuclei, a process of Ostwald ripening and a process to grow particles, that the emulsion does not substantially contain iodine when the nuclei of particles are produced, and that an iodide compd. is added in the period from just after the production of nuclei is started till the Ostwald ripening process is completed. SOLUTION: This silver halide emulsion contains silver chloride by 20-100mol% and 30-100% of the whole projection area of particles consists of planer particles having (100) planes as two principal planes parallel to each other and 2-5 of aspect ratio. The producing method of this emulsion consists of a process to produce nuclei, a process for Ostwald ripening, and a process to grow the particles. The emulsion does not substantially contain iodine when the nuclei of particles are produced, but an iodide compd. is added in the period from just after the production of nuclei is started till the Ostwald ripening process is completed. The photographic sensitive material having a silver halide emulsion layer on a base body contains the silver halide emulsion above described in the emulsion layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide emulsion, and more particularly to a method for producing a silver halide emulsion having a narrow grain size distribution and a high tabular ratio.

Secondly, it relates to a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support and an X-ray image forming method. More specifically, it has low fog, high sensitivity and high CP (covering power). The present invention relates to a photographic light-sensitive material and an X-ray image forming method.

Further, the present invention relates to a silver halide photographic light-sensitive material excellent in ultra-rapid and low replenishment processability and an X-ray image forming method.

[0004]

2. Description of the Related Art In recent years, the consumption of silver halide photographic light-sensitive materials has been increasing. For this reason, the number of developed silver halide photographic materials has been increased, and it has been required to speed up the development processing, that is, to increase the processing amount within the same time.

The above tendency can be applied to any field of silver halide photographic light-sensitive materials. For example, in the field of medical X-ray photographic light-sensitive materials, X-ray photography is performed due to a rapid increase in the number of diagnoses and an increase in inspection items. While the number of sheets is increasing, it is necessary to inform the examinee of the diagnosis result as soon as possible, and therefore rapid processing is desired. In particular, in angiography photography, intraoperative photography, and the like, it is essentially necessary to view photographs in a little time.

[0006] In order to meet the above-mentioned demands of the medical field, it is necessary to promote automation of diagnosis (imaging, transportation, etc.) and process X-ray film more rapidly. Furthermore, recently, due to strict environmental regulations, low replenishment has been promoted by reducing the amount of processing liquid waste.

When such low replenishment and ultra-rapid processing is performed,
As a matter of course, the process variation and the performance deterioration increase. Using silver chloride silver halide grains, the developing property is rapid, and the influence of the halide ions in the developer is Br ^-,
The influence of developer accumulation can be improved in that Cl ⁻ is much smaller than I ⁻ . However, silver chloride grains, on the other hand, have difficulty in obtaining sufficient sensitivity and cannot provide satisfactory performance.

In response to the demand for rapid processing, tabular silver halide grains have recently been used. Since the tabular silver halide grains have a large specific surface area, a large amount of sensitizing dye can be adsorbed, and therefore the spectral sensitivity can be increased, and the crossover light as in the X-ray photosensitive material can be remarkably reduced. At the same time, there is a feature that an image with little light scattering and high resolution can be obtained. Therefore, a silver halide photographic light-sensitive material having high sensitivity and high image quality is expected by using such tabular grains.

For a plate containing silver chloride in which the two parallel principal planes are (100) planes, see EP 534,3.
95 and US Pat. Nos. 5,264,337 and 5,32.
No. 0,938, etc. However, these tabular grains have a wide distribution, and the number of grains having a shape other than tabular grains (rod-like grains, multiple twin grains, etc.) is large,
Moreover, since the sensitivity is still low, practical performance cannot be obtained.

Further, a medical X-ray image is usually formed by combining a fluorescent intensifying screen and an X-ray photosensitive material.
In addition to the image quality of the light-sensitive material itself, the influence of the fluorescent intensifying screen on the radiation image is very large.

The combination of the fluorescent intensifying screen and the silver halide photographic light-sensitive material to be used in X-ray photography is not particularly specified, but when high-sensitivity photography is required, for example, in the lumbar spine. In photographing, head angiography, magnifying, etc., it is usual to use a high-light emitting intensifying screen in combination with a standard or high-sensitivity silver halide photographic light-sensitive material. When image quality is particularly important, it is common to use a high-sensitivity intensifying screen in combination with a standard-sensitivity silver halide photographic light-sensitive material for simple chest radiography, gastric contrast radiography, bone photography, etc. Is. Therefore, the combination of the high-sensitizing intensifying screen and the photosensitive material lowers the sharpness of the image, while the combination of the low-sensitizing intensifying screen and the photosensitive material results in the low sensitivity.

Japanese Unexamined Patent Publication (Kokai) No. 3-21898 discloses a method for improving sharpness and graininess by increasing the packing density of phosphors in a fluorescent intensifying screen. Regarding X-ray light-sensitive materials, by combining X-ray light-sensitive materials having silver halide emulsion layers with different photographic characteristics on the front and back and fluorescent intensifying screens with different front and back, crossover light is cut and sharpness is improved. Japanese Patent Application Laid-Open No. 2-266344 and the like, in which the exposure tolerance is increased and the tolerance to exposure variation is improved, are disclosed. This technique aims to obtain various image contrasts by changing the combination with the fluorescent intensifying screen.
Practically, the graininess is deteriorated and the diagnosability is deteriorated.

Conventionally, image graininess, sharpness and contrast have been mentioned as factors that greatly affect the image quality of medical X-ray images. Regarding the graininess, for example, SR-G which is a standard light-sensitive material and SRO-250 which is a standard fluorescent intensifying screen (both are manufactured by Konica Corporation).
In the region where the tube voltage of the X-ray generating tube is 110 kVp or more, which is a normal chest imaging condition, 50% or more of the granularity deterioration is based on the X-ray quantum mottle. This greatly deteriorates the graininess and image quality of X-ray photographs. Further, in the case of a combination using a high-sensitivity X-ray film, the quantum mottle is further increased and the image quality is deteriorated.

In order to improve the image quality of X-ray photography, it is necessary to reduce the quantum mottle and maintain and improve the sharpness. This is because when the crossover light of the X-ray photosensitive material itself is cut to improve the sharpness, the image quality is not necessarily improved due to the deterioration of the graininess corresponding to the sharpness improvement. Therefore, as described above, Japanese Patent Laid-Open No. 3-218
As disclosed in Japanese Patent No. 98, a method of increasing the packing density of the phosphor of the radiation fluorescent intensifying screen to improve the sharpness and graininess is used.

In the case where a light-sensitive material in which the crossover light is largely cut in combination with a fluorescent intensifying screen having a phosphor filling rate of 66% or less is used, a phenomenon in which the graininess of the improved sharpness is deteriorated occurs. . Therefore, the crossover light of the X-ray photosensitive material itself is designed to exceed 20% to balance the image quality of graininess and sharpness. But get X
The image quality of the line photograph image is not sufficient, and further improvement has been desired.

[0016]

In order to solve the above problems, the first object of the present invention is to provide a method for producing a silver halide emulsion having a narrow grain size distribution and a high tabular ratio.

A second object is to provide a silver halide photographic light-sensitive material having low fog, high sensitivity and high CP, and an X-ray image forming method. Further, the present invention provides a silver halide photographic light-sensitive material excellent in ultra-rapid and low replenishment processability and an X-ray image forming method.

[0018]

The above object of the present invention is achieved by the following means.

The silver chloride content is 20 to 100 mol%, and 30 to 100% of the total projected area is tabular grains having two parallel main planes (100) planes and an aspect ratio of 2 or more. In a method for producing a silver halide emulsion, the production method includes a nucleation step, an Ostwald ripening step,
And a grain growth step, which does not substantially contain iodine at the time of nucleation of the grain, and an iodide is added between immediately after the nucleation of the grain and before the completion of the Ostwald ripening step. Method for producing silver emulsion.

A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, characterized in that the emulsion layer contains the silver halide emulsion described in the above item. Photographic material.

In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, the silver halide grains contained in the emulsion layer have a silver chloride content of 20 to 10
0% by mole, 30 to 100% of the total projected area has two parallel main planes (100), and an aspect ratio of 2
A silver halide photographic light-sensitive material, characterized in that it is a tabular grain of No. 50 to 50, and is a circular shape having a linear portion ratio of the main plane of the grain of 0 to 3/4.

The silver halide photographic light-sensitive material described in the above item or item is a double-sided light-sensitive material,
45-100 for X-rays with a linear energy of 80 kVp
%, The filling rate of the phosphor is 68 to 90%,
An X-ray image forming method characterized in that imagewise exposure is performed by irradiating X-rays with a fluorescent intensifying screen having a phosphor thickness of 135 to 200 μm.

In the method for forming an image by irradiating X-rays using the fluorescent intensifying screen and the silver halide photographic light-sensitive material described in the above item, the silver halide photographic light-sensitive material is
An X-ray image forming method comprising processing with an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

In the X-ray image forming method described in the above item or item, the silver halide photographic light-sensitive material is a developer containing a compound represented by the general formula (1) and / or
Alternatively, an X-ray image forming method is characterized in that processing is carried out by an automatic developing machine using a developing replenisher.

In the X-ray image forming method described in any one of the above items 1 to 3, the silver halide photographic light-sensitive material is processed with an automatic processor for a total processing time of 10 to 25 seconds. X-ray image forming method.

The X-ray image forming method as described in the above item, wherein the replenishing amount of the developing solution and / or the fixing solution is 10 to 200 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material.

Hereinafter, the present invention will be described specifically.

[Silver Halide Grains] Silver halide grains are generally produced and used in the form of a silver halide emulsion containing the grains. The silver halide emulsion of the present invention has a silver chloride content of 20 to 100 mol%, and a total projected area of 30 to 1
00% is a tabular grain having two parallel principal planes (100) planes and an aspect ratio of 2 to 50. More preferably, the silver chloride content is 30 to 70 mol%. More preferably, tabular grains satisfying the above conditions account for 50 to 100% of the total projected area. The main plane as referred to herein is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the aspect ratio is the area of the plane forming the main plane of grains. It is the ratio of the thickness between the principal planes to the edge length of the corresponding square. The edge length of the main plane is, for example, 1 for the particles with an electron microscope.
It is obtained by enlarging the image at a magnification of 10,000 to 50,000 and measuring the edge length of the particles on the print or the area at the time of projection. (The number of measured particles is assumed to be 1000 or more indiscriminately.) The particle thickness can also be obtained by actually measuring an electron micrograph. The fact that the principal plane is the (100) plane can be examined by an electron diffraction method or an X-ray diffraction method. Generally, the shape of the main plane having the (100) plane is a parallelogram, which can also be confirmed by observing an electron micrograph.

The silver halide photographic emulsion of the present invention comprises (a)
A step of introducing tabular grains by introducing a silver salt and a halide salt into a dispersion medium containing substantially no iodine, (b)
Subsequent to nucleation, Ostwald ripening under the condition of maintaining the (100) major surface of the tabular grain, (c) grain growing to a desired grain size and silver chloride content, Is prepared. The silver halide photographic emulsion of the present invention is prepared by adding iodide immediately after the initiation of nucleation to the end of the Ostwald ripening step among the above steps. The more preferable addition time is from immediately after the nucleation to the start of Ostwald ripening. Here, the time of nucleation means from the time when the silver salt is introduced into the dispersion medium to the end of the addition of 1/10 of the total amount of the added silver salt. In the present invention, the iodide is used immediately after this in the Ostwald ripening step. Is added until the end of.

The iodide added here may be added as iodide ions in the solution or as silver iodide fine particles. These iodides are added to the dispersion medium in an amount of 0.05
It is preferable to maintain the content at 10 mol%. When it is 10 mol% or more, rapid processability is impaired due to iodide ions taken in the grains. In practice, the amount of iodide required to produce the tabular grains of this invention is from 0.05 to 5 mol%.
Is preferred.

The double jet method (simultaneous mixing method) is preferably used as a method of reacting a silver salt and a halide salt during nucleation. The simultaneous mixing method is also used during grain growth, but as one type of the simultaneous mixing method, a method of keeping the pAg in a liquid phase in which silver halide is formed constant, that is, a so-called controlled double jet method may be used. it can. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

As a particle forming condition, it is preferable to adjust the pCl of the dispersion medium at the time of nucleation to 0.5 to 3.5.
It is more preferably adjusted to 1.5 to 3.0. The amount of binder in the dispersion medium during nucleation is preferably 0.25% by weight or more. A more preferable range is 0.5 to 10% by weight. Nucleation begins when the silver salt solution is introduced into the dispersion medium. The silver salt addition rate during nucleation is preferably in the range of 0.005 to 1.0 mol / min of silver salt per liter of the dispersion medium.

In the silver halide emulsion of the present invention, part or all of the steps during grain formation may be a grain formation step by supplying fine silver halide grains. Since the particle size of the fine particles governs the supply rate of the halide ions, the preferred particle size varies depending on the size and halogen composition of the silver halide grains of the host, but those having an average equivalent sphere diameter of 0.3 μm or less are used. More preferably, it is 0.1 μm or less. In order for the fine particles to be laminated on the host particles by recrystallization, the size of the fine particles is preferably smaller than the equivalent spherical diameter of the host particles,
More preferably, it is 1/10 or less of the equivalent spherical diameter. In a more preferred embodiment, the shape of the main plane of the particles is a circular shape having a linear portion ratio of 0 to 3/4.

In the present invention, when grains are formed by a fine grain emulsion, iodide can be added at any time before the end of the step of Ostwald ripening. Particularly preferably, it is before the addition of the fine grain emulsion. However, when the nucleation step is provided, iodide must be added immediately after the nucleation and before the Ostwald step is completed.

The main outer surface of the circular tabular grain of the present invention is circular, but it need not be a perfect circle. That is, it may have a linear portion in part. That is, when the main plane has a shape such that the corners of the parallelogram are rounded, the straight line portion of the side is extended and the distance between the intersection of the straight line portion of the adjacent side and the line The actual straight line ratio is 0
It may be 3/4. Of course, a circular particle having no linear portion (a linear ratio of zero) may be used. The linear portion ratio is preferably 0 to 1/2.

The circular tabular grains of the present invention may be rounded at the corners of the parallelogram of the main plane, or may be made convex by growing the central portion of the side. The degree to which the edges of the parallelogram are rounded depends on the temperature, pCl value, time, etc. during Ostwald ripening. Specifically, by changing the aging conditions and observing the electron micrograph image of the obtained particles. , You can set the conditions.

The surface on which the screw dislocation is formed at the nucleation stage has a higher growth rate than the surface on which the screw dislocation is not formed in the subsequent grain growth process. Therefore, cubic x
The grain in which the screw dislocation is formed on the surface in the y direction is a tabular grain in which the main plane of the present invention is the (100) plane. By further subjecting these tabular grains to Ostwald ripening, the side in which the screw dislocation is introduced can be made convex. The tabular grains obtained by the production method of the present invention can be made into a circular shape having a linear portion ratio of the main plane of 0 to 3/4 by further performing Ostwald ripening.

[Desalting] The silver halide emulsion used in the practice of the present invention is a Noudel washing method in order to remove the soluble salts after the growth of silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. The flocculation sedimentation method and the like may be used, and a preferred washing method is, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or JP-A-2-7037. Exemplified G- which is a polymer flocculant of
3, a desalting method using G-8 and the like can be mentioned.
Also, Research Disclosure (RD) Vol.
102, 1972, October issue, Item 10208 and Vol. 131, 1975, March Issue, Item 1312
Desalting may be performed using the ultrafiltration method described in 2.

[Binder] In the silver halide emulsion according to the present invention, various hydrophilic colloids for wrapping silver halide are used as a binder. For this purpose, gelatin and synthetic polymers such as polyvinyl alcohol and polyacrylamide, and photographic binders such as colloidal albumin, polysaccharides and cellulose derivatives can be used.

[Chemical Ripening] The silver halide emulsion used in the present invention can be chemically ripened. There are no particular restrictions on the conditions of the chemical aging step, such as pH, pAg, temperature, time, etc., and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance is used. The reduction sensitization method used, gold and other noble metal sensitization methods using a noble metal can be used alone or in combination. Among them, sulfur sensitization method, selenium sensitization method, tellurium sensitization method, reduction sensitization method, etc. Is preferably used.

[Selenium Sensitization] In the case of selenium sensitization, the selenium sensitizer used includes a wide variety of selenium compounds. For example, in this regard, US Pat. No. 1,574,944
JP-A-60-150046, JP-A-4-2583
No. 2 etc. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N ′).
-Triethylselenourea, N, N, N'-trimethyl-
N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-nitrophenylcarbonylselenourea, etc.), selenoketones ( For example, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutycin). Rate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

Specific examples of the technique of using these selenium sensitizers are described in the above-mentioned patents and H. E. FIG. Spencer et al. Jour
nal of Photographic Science
It is also disclosed in scientific literatures such as Ce magazine, Vol. 31, pp. 158-169 (1983).

[Tellurium sensitization] Tellurium sensitizers and sensitizing methods are described in US Pat.
No. 204640, No. 4-333043, etc. Useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'-dimethyl-N. ′ -Phenyl tellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-
Examples thereof include diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, and isotellurocyanates.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

[Reduction sensitization] It is also preferable to carry out so-called reduction sensitization on the surface of the grain by placing it in an appropriate reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof. Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

[Spectral Sensitization] The silver halide emulsion used in the practice of the present invention may be spectrally sensitized with cyanine dyes and the like. The sensitizing dye may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for supersensitization.

[Various Additives] In the silver halide photographic light-sensitive material using the silver halide emulsion of the present invention, various photographic additives are used in the steps before and after physical ripening or chemical ripening of the silver halide emulsion. You can Examples of the compound that can be used in such a step include Research Disclosure (RD) 17643, p23 to 29, (R
D) 18716 (November, 1979) p648-65.
1 and (RD) 308119 (December 1989) p.
The various compounds described in 996-1009 are mentioned.

[Support] Examples of the support used in the silver halide photographic light-sensitive material of the present invention include those described in the above RD, and a suitable support is a plastic film or the like. The surface of the body may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation. Then, the emulsion according to the present invention can be coated on both sides of the support thus treated.

[Coating] The silver halide photographic light-sensitive material of the present invention may be optionally provided with an antihalation layer, an intermediate layer, a filter layer and the like. In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method, or the like can be used. See Research Disclosure, Chapter 17
6, p. 27-28 "Coating process"
dures "section.

[Fluorescent intensifying screen] When the present invention is applied to medical X-ray radiography, for example, a sensitizing substance containing a phosphor that generates near-ultraviolet light or visible light as a main component by exposure to penetrating radiation. Paper is used. This is brought into close contact with both surfaces of a light-sensitive material obtained by coating the emulsion of the present invention on both surfaces and exposed. Preferred phosphors used in the intensifying screen according to the present invention include those shown below.

Tungstate phosphor (CaWO ₄ ,
MgWO ₄ , CaWO _4, Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor (Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S: T)
b, La ₂ O ₂ S: Tb, [Y. Gd] ₂ O ₂ S: Tb,
[Y. Gd] O ₂ S: Tb. Tm, etc.), terbium-activated rare earth phosphate-based phosphor (YPO ₄ : Tb, GdPO ₄ : T
b, LaPO ₄ : Tb, etc.), terbium-activated rare earth oxyhalide phosphor (LaOBr: Tb, LaOB)
r: Tb. Tm, LaOCl: Tb, LaOCl: T
b. Tm, LaOCl: Tb. Tm. LaOBr: Tb
GdOBr: TbGdOCl: Tb), thulium-activated rare earth oxyhalide-based phosphor (LaOBr: T
m, LaOCl: Tm, etc.), barium sulfate-based phosphor (B
aSO ₄ : Pb, BaSO ₄ : Eu ²⁺ , [Ba. Sr] S
O ₄ : Eu ^2+, etc.), a divalent eurobium-activated alkaline earth metal phosphate-based phosphor ([Ba ₂ PO ₄ ] ₂ : Eu
^2+, etc.), divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor (BaFCl: Eu ²⁺ , BaFB)
r: Eu ²⁺ , BaFCl: Eu ²⁺ . Tb, BaFBr:
Eu ²⁺ . Tb, BaF ₂ , BaCl, KCl: Eu ²⁺ ,
[Ba / Mg] F ₂ / BaCl / KCl: Eu ^2-, etc.),
Iodide phosphors (CsI: Na, CsI: Tl, Na
I, KI: Tl, etc.), sulfide-based phosphor (ZnS: Ag)
[Zn. Cd] S: Ag, [Zn. Cd] S: Cu,
[Zn. Cd] S: Cu. Al, etc.), hafnium phosphate-based phosphors (HfP ₂ O ₇ : Cu, etc.), tantalate-based phosphors (YTaO ₄ , YTaO ₄ : Tm, YTaO ₄ : Nb,
[Y. _{Sr] TaO 4: Nb, GdTaO} 4: Tm, Gd
₂ O ₃ .Ta ₂ O ₅ .B ₂ O ₅ : Tb, etc., but the phosphors used in the present invention are not limited to these, and fluorescence that emits light in the visible or near-ultraviolet region upon irradiation with radiation. Any body can be used.

The intensifying screen of the present invention is preferably filled with a phosphor in a gradient particle size structure. In particular, it is preferable to coat large-sized phosphor particles on the surface protective layer side, and to coat small-sized phosphor particles on the support side.
2.0 μm, and those having a large particle diameter are preferably in the range of 10 to 30 μm.

The production of the intensifying screen includes the step of forming a phosphor sheet composed of a binder and a phosphor, placing the phosphor sheet on a support, and compressing at a temperature above the softening temperature or melting point of the binder. However, it is preferably manufactured in the step of adhering the phosphor sheet to a support.

The phosphor sheet to be the phosphor layer of the intensifying screen was coated with a coating solution prepared by uniformly dispersing the phosphor in a binder solution, and dried on a temporary support for forming the phosphor sheet. Then, it can be manufactured by peeling from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and the mixture is stirred and mixed to prepare a coating solution in which the phosphor is uniformly dispersed in the binder.

The binder has a softening temperature or melting point of 3
A thermoplastic elastomer at 0 to 150 ° C. is used alone or together with another binder. Since the thermoplastic elastomer has elasticity at room temperature and becomes fluid when overheated, it is possible to prevent the phosphor from being damaged by the pressure at the time of compression. Examples of the thermoplastic elastomer are selected from the group consisting of polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber. At least one thermoplastic elastomer may be mentioned.

The mixing ratio of the thermoplastic resin in the binder is
The binder may be 10% by weight or more and 100% by weight or less.
Preferably, it consists of 0% by weight of a thermoplastic elastomer.

Examples of the solvent for preparing the coating liquid include lower alcohols such as methanol, ethanol, n-propanol and n-butanol, chlorine atom-containing hydrocarbons such as methylene chloride and ethylene chloride, acetone, methyl ethyl ketone and methyl isobutyl ketone. And ketones, esters of lower fatty acids and lower alcohols such as methyl acetate, ethyl acetate and butyl acetate, dioxane, ethers such as ethylene glycol monoethyl ester and ethylene glycol monomethyl ester, and mixtures thereof.

The mixing ratio of the binder and the phosphor in the coating solution varies depending on the characteristics of the target intensifying screen, the kind of the phosphor, etc., but generally the mixing ratio of the binder and the phosphor is 1: 1 to 1. It is preferable to select from the range of: 100 (weight ratio).
The coating liquid includes a dispersant for improving the dispersibility of the phosphor in the coating liquid, or a plasticizer for improving the binding force between the binder and the phosphor in the phosphor layer after formation. Various additives may be mixed.

Examples of the dispersant include phthalic acid, stearic acid, caproic acid and lipophilic surfactants.

Examples of the plasticizer include triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, and other phosphoric acid esters, diethyl phthalate, dimethoxyethyl phthalate, and other phthalic acid esters, ethyl phthalyl glycolate, and butyl phthalbutyl glycolate. Examples thereof include glycolic acid esters, polyesters of triethylene glycol and adipic acid, polyesters of polyethylene glycol and aliphatic dibasic acids such as polyesters of diethylene glycol and succinic acid, and the like.

The coating solution containing the phosphor and the binder prepared as described above is uniformly applied to the surface of the temporary support for sheet formation to form a coating film of the coating solution. As the coating means, for example, a doctor blade, a roll coater, a knife coater or the like can be used.

As the temporary support, those made of various materials such as glass, wool, cotton, paper and metal can be used, but a sheet or roll which is flexible in handling as an information recording material. Those that can be processed into are preferred. From this point, for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, plastic film such as polycarbonate film, aluminum foil, metal sheet such as aluminum alloy foil, general paper and, for example, for photography Base paper, coated paper or printing base paper such as art paper, baryta paper, resin coated paper, Belgian patent 78
Particularly preferred are processed papers such as paper sized with polysaccharide or the like described in US Pat. No. 4,615, pigment paper containing a pigment such as titanium dioxide, and paper sized with polyvinyl alcohol.

A coating solution for forming a phosphor layer is applied onto a temporary support, dried, and then peeled from the temporary support to obtain a phosphor sheet which becomes a phosphor layer of an intensifying screen. Therefore, the surface of the temporary support is
It is preferable to apply a release agent in advance so that the formed phosphor sheet can be easily released from the temporary support.

Will be described. A support for setting the phosphor formed as described above is prepared. This support can be arbitrarily selected from the materials listed for the temporary support.

Known intensifying screens are provided with an undercoat layer for imparting adhesiveness by coating a high molecular substance such as gelatin on the surface of the support in order to strengthen the bond between the support and the phosphor layer, and to improve sensitivity and image quality. In order to improve (sharpness and graininess), a light reflecting layer made of a light reflecting substance such as titanium dioxide or a light absorbing layer made of a light absorbing substance such as carbon black may be provided.

The support used in the present invention can also be provided with these various layers, and the constitution thereof can be arbitrarily selected according to the desired purpose and use of the intensifying screen.

The phosphor sheet obtained by the above is placed on a support, and the phosphor sheet is adhered on the support while being compressed at the softening temperature or the melting point or higher of the binder. In this way, it is possible to spread the sheet thinly by utilizing the method of crimping the phosphor sheet on the support without previously fixing it, and not only preventing the phosphor from being damaged,
A higher phosphor filling rate can be obtained with the same pressure as compared with the case where the sheet is fixed and pressed. Examples of the compression apparatus used for the compression treatment of the present invention include generally known ones such as calender rolls and hot presses. For example, the compression treatment using a calender roll is performed by placing the phosphor sheet obtained on a support and passing the phosphor sheet at a constant speed between rollers heated to a temperature higher than the softening temperature or melting point of the binder. However, the compression device used in the present invention is not limited to these, and any device can be used as long as it can compress the sheet while heating it. The compression pressure is preferably 50 kg / cm ² or more.

Usually, in the intensifying screen, a transparent protective film for physically and chemically protecting the phosphor layer is provided on the surface of the phosphor layer on the side opposite to the side in contact with the support. It is preferable to install such a transparent protective film also in the intensifying screen of the present invention. The thickness of the protective film is generally 0.1 to 20.
in the range of μm. For the transparent protective film, for example, a cellulose derivative such as cellulose acetate or nitrocellulose, or a synthetic polymer substance such as polymethyl methacrylate, polyethylene terephthalate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer is suitable. It can be formed by a method of coating a solution prepared by dissolving in a solvent on the surface of the phosphor layer. Or polyethylene terephthalate, polyethylene naphthalate, polyethylene,
A plastic sheet made of polyvinylidene chloride, polyamide, etc., and a protective film-forming sheet such as a transparent glass plate are separately prepared and are adhered to the surface of the phosphor layer by using an appropriate adhesive. You can

As the protective layer used in the intensifying screen of the present invention, a film formed of a coating film containing a fluorine resin soluble in an organic solvent is particularly preferable. The fluorine-based resin refers to a polymer of an olefin containing fluorine (fluoroolefin) or a copolymer containing an olefin containing fluorine as a copolymer. The film formed by the coating film of the fluorine-based resin may be cross-linked. The advantage of a protective film made of a fluorine-based resin is that dirt such as a plasticizer that comes out of a film or the like when coming into contact with another material or an X-ray film hardly penetrates into the protective film, so that the dirt can be easily removed by wiping or the like. There is.

As a material for forming a protective film, when an organic solvent-soluble fluorine resin is used, this resin was dissolved in an appropriate solvent to prepare the resin. That is, the protective film is formed by uniformly applying a protective film-forming material coating liquid containing an organic solvent-soluble fluorine-based resin on the surface of the phosphor layer using a doctor blade or the like, and drying the coating. The formation of this protective film may be performed simultaneously with the formation of the phosphor by simultaneous multilayer coating.

The fluorine-based resin is a polymer of a fluorine-containing olefin (fluoroolefin) or a copolymer containing a fluorine-containing olefin as a copolymer component, such as polytetrafluoroolefin, polychlorotrifluoroethylene, poly Examples thereof include ethylene fluoride, polyvinyl fluoride, polyvinylidene fluoride, a tetrafluoroethylene-hexafluoropropylene copolymer and a fluoroolein-vinyl ether copolymer. Fluorine-based resins are generally insoluble in organic solvents, but a copolymer containing a fluoroolefin as a copolymer component becomes soluble in an organic solvent due to a constitutional unit other than the fluoroolefin to be copolymerized. The protective layer can be easily formed by coating the phosphor layer with a solution prepared by dissolving in, and drying. Examples of such a copolymer include a fluoroolefin-vinyl ether copolymer. Also, polytetrafluoroethylene and its modified products are soluble in a suitable fluorine-based organic solvent such as a perfluoro solvent, and thus are protected by coating in the same manner as the copolymer containing the above-mentioned fluoroolefin as a copolymer component. A film can be formed.

The protective film may contain a resin other than a fluorine-based resin, and may contain a crosslinking agent, a hardener, an anti-yellowing agent, and the like. However, in order to sufficiently achieve the above-mentioned object, the content of the fluorine-based resin in the protective film is preferably 30% by weight or more, more preferably 50% by weight.
It is at least wt%, most preferably at least 70 wt%. Examples of the resin other than the fluorine-based resin contained in the protective film include polyurethane resin, polyacrylic resin, cellulose derivative, polymethylmethacrylate, polyester, and epoxy resin.

The protective film of the intensifying screen used in the present invention may be formed from a coating solution containing either one or both of a polysiloxane skeleton-containing oligomer and a perfluoroalkyl group-containing oligomer. The polysiloxane skeleton-containing oligomer has, for example, a dimethylpolysiloxane skeleton, and has at least one functional group,
For example, it preferably has a hydroxyl group, and preferably has a molecular weight of 500 to 100,000. In particular, the molecular weight is preferably in the range of 1000 to 100000, more preferably 3000 to 1000.
00 range. The oligomer containing a perfluoroalkyl group such as a tetrafluoroethylene group preferably has at least one functional group such as a hydroxyl group in the molecule and has a molecular weight of 500 to 100.
000 is preferable. Especially the molecular weight is 10
It is preferably in the range of 00 to 100,000.

If an oligomer containing a functional group is used, a cross-linking reaction occurs between the oligomer and the protective layer film forming resin at the time of forming the protective film, and the oligomer is incorporated into the molecular structure of the film forming resin. Since the oligomer is not removed from the protective layer even by operations such as repeated use of the intensifying screen for a long period of time or cleaning of the protective layer surface, the addition effect of the oligomer is effective for a long period of time. Use is advantageous. The oligomer is preferably contained in the protective layer in an amount of 0.01 to 10% by weight, and particularly preferably 0.1 to 2% by weight.

The protective layer may contain perfluoroolefin resin powder or silicone resin powder. As the perfluoroolefin resin powder or the silicon resin powder, those having an average particle diameter in the range of 0.1 to 10 μm are preferable, and particularly preferably the average particle diameter is 0.3 to 5 μm.
m. These perfluoroolefin resin powders or silicon resin powders are preferably contained in the protective layer in an amount of 0.5 to 30% by weight, and further in an amount of 2 to 20% by weight, based on the weight of the protective film. Is preferred, and most preferably in an amount of 5 to 15% by weight.

The protective film of the intensifying screen is preferably a transparent synthetic resin layer having a thickness of 5 μm or less formed by coating on the phosphor layer. By using such a thin protective layer,
Since the distance from the phosphor of the intensifying screen to the silver halide emulsion layer becomes short, it contributes to the improvement of the sharpness of the obtained X-ray image.

The filling rate of the phosphor in the present invention can be obtained from the following formula from the porosity of the phosphor layer formed on the support.

[0078]

(Equation 1)

V: Total volume of the phosphor layer Vair; Air volume in the phosphor A; Total weight of the phosphor px; Density of the phosphor py; Density of the binder pair; Air density a; Weight of the phosphor b Weight of binder Further, in the formula (1), since the pair is almost 0, the formula (1) can be approximately represented by the following formula (2).

[0080]

(Equation 2)

However, V, Vair, A, px, py,
The definitions of a and b are the same as in the formula (1).

In the present invention, the porosity of the phosphor layer is calculated by the equation (2). The filling rate of the phosphor is given by the following equation (3).
Can be obtained by

[0083]

(Equation 3)

However, the definitions of V, A, px, py, a and b are the same as in the formula (1).

The intensifying screen of the present invention has an intrinsic filtration of 45% or more with respect to X-rays having an X-ray energy of 80 kVp in an X-ray generator having an aluminum equivalent to 2.2 mm, depending on the filling rate and thickness of the phosphor. It is preferable to show the absorption amount of It is more preferably 50% or more. The X-ray absorption amount of the intensifying screen can be measured by the following method.

X-rays generated from a tungsten target tube operated at 80 kVp with a three-phase power supply, were made to have a thickness of 3
mm of aluminum plate was transmitted, and it was made to reach the intensifying screen of the sample fixed at the position of 200 cm from the tungsten anode of the target tube, and then X was transmitted through the intensifying screen.
The amount of rays is measured at a position 50 cm after the phosphor layer of the intensifying screen using an ionization dosimeter, and the amount of absorbed X-rays is obtained. In addition, as a reference, the X-ray dose measured by the above-described measuring device without transmitting the intensifying screen can be obtained.

The thickness of the phosphor is 135 μm or more and 200 μm
The following is preferred. More preferably, the filling rate of the phosphor at this time is 65% or more.

The production of the fluorescent intensifying screen of the present invention is described in JP-A-6-
It can be prepared according to the method disclosed in No. 75097. That is, a phosphor, a binder, a surface protective layer,
It is preferable that the materials for the conductive layer and the steps for producing them in combination are prepared according to the method disclosed in JP-A-6-75097. Further, it is preferable that large particles are arranged near the surface protective layer of the phosphor by a multilayer coating method or the like.

[Processing] The processing of the silver halide photographic light-sensitive material of the present invention is carried out by, for example, the above-mentioned RD-17643, XX to XXI.
p29-30 or XX-XXI p101 of the same 308119
The treatment with the treatment liquid as described in 1 to 1012 can be performed.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-aminophenol) and the like. They can be used alone or in combination. In the developer, a known agent such as a preservative, an alkali agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone agent, a water softener, and a dissolution aid can be used. A viscosity imparting agent may be used as necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. Other preservatives, pH adjusters,
It may contain a water softener or the like.

[Solid Processing Agent] In the present invention, the developing treatment can be carried out by an automatic developing machine having a mechanism for supplying the solid processing agent to the processing tank. As the supply means of the automatic processor, for example, in the case where the solid processing agent is a tablet, an actual developing machine 63
-137873, 63-97522, Actual Kaihei 1-
Although there is a known method such as 85732, any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powder, it is used in JP-A-62-81964 and 63-84151.
Known methods include, but are not limited to, the gravity drop method described in JP-A-1-292375, and the method using a screw or screw described in JP-A-63-105159 and 63-195345. is not. The place where the solid processing agent of the present invention is put may be in a processing tank, but preferably, it is in communication with a processing section for processing a light-sensitive material and a processing solution is flowing between the processing section and the processing section. In addition, a structure in which a fixed amount of the processing liquid is circulated between the treatment unit and the dissolved components moves to the treatment unit is preferable. The solid processing agent is preferably added to the temperature-controlled processing liquid.

In the developer used in the development processing method of the present invention, as developing agents, dihydroxybenzenes, aminophenols and pyrazolidones described in JP-A-6-13859 as well as JP-A-5-165161 are described. Reductones are also used. Pyrazolidones used, particularly those substituted at the 4-position (dimesone, dimesone S, etc.)
Is particularly preferable because it is less water-soluble and has little change over time in the solid processing agent itself. As a preservative, an organic reducing agent can be used as a preservative in addition to the sulfite described in Japanese Patent Application No. 6-13859. In addition, Japanese Patent Application No. 4-586323 (20
Page 21) or a bisulfite adduct of a hardener described in page 21).

Further, as a silver sludge-preventing agent, JP-A 5-2 is used.
89255, JP-A-6-308680 (general formula [4
-A] [4-b]) is also preferred. Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

An amine compound may be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

It is necessary to use a buffering agent in the developer, and as the buffering agent, sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, o-hydroxybenzoic acid Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. Can be mentioned.

As the development accelerator, Japanese Patent Publication No. 37-160
Nos. 88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; No. 50-15554
Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429. US Patent 2,61
P-aminophenols described in U.S. Pat. Nos. 0,122 and 4,119,462; U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253. No. 919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like. 42-25201
No. 3,128,183, JP-B-41-11
Nos. 431 and 42-23883 and U.S. Pat.
No. 2,501 and other polyalkylene oxides,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

As the antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be exemplified by 1-phenyl-5-mercaptotetrazole as a typical example.

Further, in the developer composition used in the present invention, if necessary, methyl cellosolve, methanol,
Acetone, dimethylformamide, cyclodextrin compound, and other JP-B-47-33378, 44-9
No. 509 can be used as an organic solvent for increasing the solubility of a developing agent.

Further, various additives such as stain inhibitors, sludge inhibitors, and multi-layer effect accelerators can be used.

A compound known as a fixing agent can be added to the fixing agent used in the present invention. Fixing agent, chelating agent, p
An H buffer, a hardener, a preservative and the like can be added, and these are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-11
Those described in 3632 (pages 2 to 4) can be used. In addition, as a hardener, a chelating agent described in Japanese Patent Application No. 4-586323 (page 20), a bisulfite adduct of the hardener described in the same (page 21), or a known fixing accelerator can be used.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify and add the starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The automatic developing machine is equipped with a mechanism for applying water or a rinse solution of an acid solution having no fixing ability to the light-sensitive material during the steps of development, fixing and washing with water (Japanese Patent Laid-Open No. HEI 3).
-264953) may be used. Further, a device capable of adjusting a developing solution and a fixing solution may be incorporated.

The light-sensitive material of the present invention can be processed by a conventional processing method using no solid processing agent.

[Compound Represented by General Formula (1)] The silver halide photographic light-sensitive material of the present invention uses a developer and / or a development replenisher containing the compound represented by the general formula (1). Can be processed by an automatic processor. Hereinafter, the compound represented by formula (1) will be described.

In the present invention, the compound represented by the general formula (1) is used in an amount of 0.005 to 0.5 per liter of the developing solution.
It is preferable to use 1 mol, more preferably 0.02 to 0.4 mol.

Next, the compound represented by the general formula (1) will be described in detail.

In the general formula (1), R ₁ and R ₂ each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. , X is a ring-forming atomic group, preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and R ₁ ,
_Two vinyl carbons substituted by R ₂ and a carbonyl carbon together form a 5- or 6-membered ring. Furthermore, specifically, R
₁ and R ₂ each independently include a hydroxy group, an amino group (having a substituent having an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-butyl group, or a hydroxyethyl group) as a substituent. ), An acylamino group (acetylamino group, benzoylamino group, etc.), an alkylsulfonylamino group (methanesulfonylamino group, etc.),
It represents an arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto group, alkylthio group (methylthio group, ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group. X is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and forms a 5- to 6-membered ring together with the two vinyl carbons and the carbonyl carbon substituted by R ₁ and R ₂ . Specific examples of X include -O-, -C (R
_{3) (R 4) -,} - C (R 5) =, - C (= O) -, - N
(R ₆₎ -, - formed by combining the N =. However, R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom,
10-substituted alkyl groups (including a hydroxy group, a carboxy group, and a sulfo group as substituents) and C 6-15 aryl groups that may be substituted (alkyl groups as substituents, halogen atoms) , Hydroxy group,
A carboxy group and a sulfo group can be mentioned), a hydroxy group, and a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Preferred examples of the 5- or 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring and a uracil ring. Specific examples of the compound represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[Treatment Time] In the present invention, ultra-rapid treatment with a total treatment time (Dry to Dry) of 10 to 25 seconds can be performed. The developing step time or developing time in the present invention is the time from the dipping of the front end of the photosensitive material to be processed in the developing tank solution of an automatic developing machine (hereinafter referred to as an automatic processor) to the immersion of the next fixing solution. The fixing time means the time from the immersion in the fixing tank liquid to the immersion in the next washing tank liquid (stabilizing liquid), and the washing time means the time of immersion in the washing tank liquid. The drying time is usually 35 to 100 ° C., preferably 40 to 8 for an automatic processor.
A drying zone to which hot air of 0 ° C. is blown is provided, and it refers to a time in the drying zone.

In the development processing of the present invention, the development time is 3 to 1
5 seconds, preferably 3 to 10 seconds, development temperature is 25 to 50 ° C
Is preferable, and 30 to 40 ° C. is more preferable. The fixing temperature and time are preferably 20 to 50 ° C. and 2 to 12 seconds, and 30 to
More preferably, it is 2 to 10 seconds at 40 ° C. Washing or stabilizing bath temperature and time are preferably 0 to 50 ° C. and 2 to 15 seconds, and 1
More preferably, it is 5 to 40 ° C. and 2 to 8 seconds. According to the method of the present invention, the developed, fixed and washed (or stabilized) silver halide photographic light-sensitive material is dried through a squeeze roller which squeezes the washing water. The drying is carried out at 40 to 100 ° C., and the drying time may be appropriately changed depending on the environmental temperature, but is usually 3 to 12 seconds, particularly preferably 40 to 80 ° C. and 3 to 8 seconds. It is more preferable to use a far infrared heater.

[Replenishing Amount] In the present invention, the replenishing amount of the developing solution and the fixing solution may be 10 to 200 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material.

In addition, various techniques used in the photographic technique can be applied to the practice of the present invention.

[0117]

Embodiments of the present invention will be described below. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example 1 (Preparation of silver iodide fine particles) Solution A1 ossein gelatin 100 g KI 8.5 g made up to 2000 ml with distilled water solution B1 AgNO ₃ 360 g made up to 605 ml with distilled water solution C1 KI 352 g made up to 605 ml with distilled water Add A1 to the reaction vessel, keep it at 40 ℃, and stir
1 and C1 were added at a constant rate by the simultaneous mixing method over 30 minutes. The pAg during the addition is 1 pAg by a conventional pAg control means.
It was kept at 3.5. The formed silver iodide has an average grain size of 0.06 μm.
It was a mixture of β-AgI and γ-AgI of m. This emulsion is called a silver iodide fine grain emulsion.

(Preparation of Tabular Emulsion) <Preparation of Comparative Emulsion EM-A> Solution A2 Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Distilled water 7500 ml Solution B2 Silver nitrate 1500 g Distilled water 2500 ml Solution C2 KI 4 g NaCl 140 g Distilled water to 684 ml Solution D2 NaCl 375 g Distilled water to 1816 ml At 40 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
To A2 in a reaction vessel having a mixing stirrer as shown in No. 58289, 684 ml of B2 and the total amount of C2 were added over 1 minute. The EAg was adjusted to 149 mV, and after aging for 20 minutes in Ostwald, the remaining total amount of B2 and the total amount of D2 were added over 40 minutes. Meanwhile, EAg was controlled at 149 mV. After the addition is completed, in order to remove excess salts, precipitation desalting is carried out, and then a gelatin solution is added and dispersed to prepare Emulsion E.
It was M-A.

<Preparation of Comparative Emulsion EM-B> In EM-A, the same procedure as in EM-A was carried out except that 0.004 mol of silver iodide fine particles described above was added in place of KI in solution A2. Emulsion EM-B was prepared.

<Preparation of Comparative Emulsion EM-C> In EM-A, except that KI added to solution A2 and solution C2 was removed and 4.625 g of KI was added to solution D2, E
Emulsion EM-C was prepared in the same manner as MA.

<Preparation of Comparative Emulsion EM-D> In EM-A, when KI added to solution A2 and solution C2 was removed and solution B2 and solution D2 were added, silver iodide fine particles 0.028 EM-A except that the molar equivalents are added simultaneously
Emulsion EM-D was prepared in the same manner as in.

<Preparation of Comparative Emulsion EM-E> Emulsion EM-E was prepared in the same manner as EM-A except that KI added to solution A2 was removed in EM-A.

<Preparation of Emulsion EM-F of the Present Invention> EM-E
In, after adding the solution B2 for 25 seconds, the solution C2
Emulsion EM in the same manner as EM-E except that
-F was prepared.

<Preparation of Emulsion EM-G of the Present Invention> Solution A3 Ossein gelatin 37.5 g NaCl 16.5 g Distilled water to 7500 ml Solution B3 Silver nitrate 1500 g Distilled water to 2500 ml Solution C3 NaCl 140 g Distilled water 674 ml Solution D3 NaCl 375 g Distilled water 1816 ml Solution E3 KI 4 g Distilled water 10 ml At 40 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
To A3 in a reaction vessel having a mixing stirrer as shown in No. 58289, 684 ml of B2 and the total amount of C2 were added over 1 minute. E3 was added simultaneously 5 seconds after the start of addition of B2 and C2. After adjusting the EAg to 149 mV and aging Ostwald for 20 minutes, the total amount of remaining B3 and total amount of D3 was 4
Added over 0 minutes. Meanwhile, EAg was controlled at 149 mV.

After the completion of addition, precipitation desalting and gelatin dispersion were carried out in the same manner as EM-A to obtain emulsion EM-G.

<Preparation of Emulsion EM-H of the Present Invention> EM-G
In place of solution E3, silver iodide fine particles of 0.024
Emulsion EM-H was prepared in the same manner as EM-G, except that the molar equivalent was added.

<Preparation of Emulsion EM-I of the Invention> EM-G
In, except that the solution E3 is added immediately after the addition of the solution B3 and the solution C3 is finished, and then Ostwald ripening is performed.
Emulsion EM-I was prepared in the same manner as EM-G.

<Preparation of Emulsion EM-J of the Present Invention> EM-H
Emulsion E was prepared in the same manner as in EM-H except that immediately after the addition of solution B3 and solution C3, 0.024 mol of silver iodide fine grains was added and Ostwald ripening was then performed.
MJ was prepared.

About 30 of the obtained emulsions EM-A to EM-J.
Table 1 shows the results of observing and measuring 00 pieces with an electron microscope and analyzing the shapes.

Further, in the preparation of the emulsions EM-A to EM-J, after mixing, ripening was further carried out at 40 ° C. and 149 mV for 1 hour to obtain EM-A 'to EM-J'.
Was prepared.

Table 1 shows the results obtained by observing and measuring about 3000 emulsions EM-A 'to EM-J' thus obtained by electron microscopy.

[0133]

[Table 1]

Example 2 (Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) The following spectral sensitizing dyes (A) and (B) were mixed in advance at a ratio of 100: 1 by 27:
A solid fine particle dispersion of the spectral sensitizing dye was obtained by adding water whose temperature was adjusted to 0 ° C. and stirring with a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes. At this time, the sensitizing dye (A) was adjusted to have a concentration of 2%.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3 , 3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride [sensitization] The obtained emulsion was subsequently subjected to spectral sensitization and chemical sensitization by the following methods.

After the emulsion was heated to 50 ° C., the sensitizing dye (A),
After adding (B) as the solid fine particle dispersion, a mixed solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and adenine are added, and further, a dispersion liquid of triphenylphosphine selenide and silver iodide fine particles are added. Aging was performed for a total of 2 hours and 30 minutes. 4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer at the end of aging
An appropriate amount of tetrazaindene (TAI) was added.

The spectral sensitizing dyes and other additives and their addition amounts (per 1 mol of AgX) are shown below.

Spectral sensitizing dye (A) 400 mg Spectral sensitizing dye (B) 4 mg Adenine 10 mg Ammonium thiocyanate 3.3 mg Chloroauric acid 50 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 4.0 mg Silver iodide fine particles 5 mmol Equivalent Stabilizer (TAI) 1000 mg A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide is added to 50
It was added to 30 kg of ethyl acetate at 0 ° C., stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was added to 38 kg of pure water.
Was dissolved in and was added with 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate. Then, these two liquids were mixed, and the peripheral speed of the dispersing blade was 4 at 50 ° C. with a high-speed stirring type disperser having a dissolver with a diameter of 10 cm.
Dispersion was performed at 0 m / sec for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. afterwards,
The dispersion was diluted with pure to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of Sample) Various additives described below were added to each emulsion to prepare emulsion coating solutions. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 6 mg t-butyl-catechol 57 mg Polyvinylpyrrolidone (molecular weight 10,000) 850 mg Sodium polystyrene sulfonate (molecular weight 600,000) 1.9 g Nitrophenyl-triphenyl phosphonium chloride 14 mg 1,3 ammonium dihydroxybenzene-4-sulfonic acid 1700mg thallium nitrate 57mg of potassium bromide 170mg colloidal silica (average particle size _{14nm) 33g n-C 4 H} 9 OCH 2 CH (OH) CH 2 n (CH 2 COOCH ₃ ) ₂ 710 mg 1-phenyl-5-mercaptotetrazole 4 mg

[0141]

[Chemical 6]

The additives used in the protective layer liquid are as follows. The amount of addition is shown in an amount per 1 g of gelatin.

Sodium-i-Amilu n-decylsulfosuccinate 8.8 mg Polymethylmethacrylate (matting agent having an area average particle size of 0.35 μm) 32 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 56 mg

[0144]

Embedded image

A sample was prepared by uniformly coating both surfaces of the above coating solution on a blue-colored polyethylene terephthalate film base having a thickness of 175 μm and subjected to undercoating, and drying. At this time, the amount of silver applied to one surface of each sample was 1.8 g / m ² , and the amount of gelatin was 0.95 g / m of the protective layer.
m ² and emulsion layer 1.7 g / m ² .

Further, the following dye (a) is dispersed as a crossover cut substance by the following method between the emulsion layer and the subbing layer, and 0.25 mg / m ^{2 of} dye per one side and the amount of gelatin are used as the crossover cut layer. The coating was carried out so as to be 0.4 g / m ² .

[0147]

Embedded image

Dispersion Method Water and a surfactant alkanol XC (alkylnaphthalene-sulfonate: manufactured by DuPont) are put in a ball mill container, a dye is added, zirconium oxide beads are put, the container is sealed, and the ball mill is dispersed for 4 days.

Then, an aqueous gelatin solution is added and mixed for 10 minutes, and the beads are removed to obtain a coating solution.

(Production of Fluorescent Intensifying Screen 1) Phosphor Gd ₂ O ₂ S: Tb (Average Particle Size 1.8 μm) 200 g Bound Polyurethane Thermoplastic Elastomer Demolac TPKL-5-2625 Solid Content 40% (Sumitomo Bayer Urethane Co., Ltd. 20 g Nitrocellulose (nitrification degree 11.5%) 2 g A methyl ethyl ketone solvent was added to the above and dispersed by a propeller mixer to prepare a coating liquid for forming a phosphor layer having a viscosity of 25 ps (25 ° C.).

(Binder / phosphor ratio = 1/22) Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose as a coating liquid for forming an undercoat layer were dispersed and mixed by adding methyl ethyl ketone, and a viscosity of 3 to 3 was obtained. A 6 ps (25 ° C) dispersion was prepared.

Thickness 250 μm in which titanium dioxide is kneaded
The polyethylene terephthalate base (support) is placed horizontally on a glass plate, and the above coating solution for forming an undercoat layer is uniformly applied on the support using a doctor blade.
The coating film was dried by gradually increasing it from 100 ° C to 100 ° C to form an undercoat layer on the support. The thickness of the coating film is 15μ
m.

Onto this, the above-mentioned phosphor layer-forming coating liquid was uniformly applied and dried to a film thickness of 240 μm using a doctor blade, and then compressed. Compression was performed using a calender roll at a pressure of 800 kgw / cm ² and a temperature of 80 ° C. After this compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example [1] of JP-A-6-75097.

As described above, the fluorescent intensifying screen 1 comprising the support, the undercoat layer, the phosphor layer and the transparent protective film was produced.

(Production of Fluorescent Intensifying Screen 2) Same as in the fluorescent intensifying screen 1 except that the phosphor layer forming coating solution is applied in a thickness of 150 μm in the production of the fluorescent intensifying screen 1 and no compression is performed. Thus, a fluorescent intensifying screen 2 comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced.

(Measurement of Characteristics of Fluorescent Intensifying Screen) (1) Measurement of Sensitivity The MRE single-sided silver halide photographic light-sensitive material manufactured by Eastman Kodak Co., Ltd. has the fluorescent intensifying screen to be measured in front of the X-ray source. A light-sensitive material and then a fluorescent intensifying screen are placed in contact with each other, and the X-ray exposure amount is changed by the distance method.
Step exposure was performed with a width of 15 mm. The exposed silver halide photographic light-sensitive material was subjected to development processing by the method described below for the method described in "Measurement of characteristics of silver halide photographic light-sensitive material" to obtain a measurement sample.

The density of the measurement sample was measured with visible light to obtain a characteristic curve. The sensitivity was represented by the reciprocal of the X-ray exposure amount to obtain Dmin + density of 1.0, and was represented by a relative sensitivity with the fluorescent intensifying screen 1 being 100 (reference value).

(2) Measurement of X-ray Absorption Amount of X-ray generated from a tungsten target tube corresponding to 2.2 mm of aluminum with intrinsic filtration operated at 80 kVp with three-phase power supply was measured on an aluminum plate having a thickness of 3 mm. Permeate and 2 from the tungsten anode of the target tube
To reach the sample fluorescent screen fixed at the position of 00 cm,
Then, the X-ray dose transmitted through the intensifying screen was measured at a position 50 cm behind the phosphor layer of the fluorescent intensifying screen using an ionizing dosimeter, and the amount of X-ray absorption was determined. In addition, as a reference, X at the above measurement position measured without passing through the fluorescent intensifying screen
Dose was used.

The sensitivity of each obtained fluorescent intensifying screen, X
The measured values of the linear absorption amount are shown below.

X-ray absorption amount Phosphor filling rate Phosphor thickness Sensitivity Fluorescent intensifying screen No. (%) (%) (Μm) 1 55 72 154 100 2 37 65 65 61 61 <Evaluation of sensitometry> The obtained photosensitive material sample was sandwiched between fluorescent intensifying screens 1 and 2, and penetrometer B type (Konica Medical Co., Ltd.) was used. Manufactured by SRX-503 after X-ray irradiation
Development temperature of 35 ° C with SR-DF processing solution using an automatic processor
The total treatment time was 45 seconds (all were manufactured by Konica Corporation) (treatment 1). At this time, the replenishment rate of the processing solution was 210 ml / m ^{2 for} both the developing solution and the fixing solution.

The sensitivity was shown as a relative value with the reciprocal of the X-ray exposure amount required to obtain the density of Sample 1 being +1.0 as the minimum density.

<Evaluation of Covering Power (CP)> After exposing each sample to the maximum density, the same developing treatment as in the evaluation of sensitometry was performed. The silver amount (g / m ² ) of the obtained sample was measured by a fluorescent X-ray analysis method, and the concentration was divided by the silver amount to obtain the covering power.

Covering power (CP) = maximum density / silver amount × 100 <Evaluation of ultra-rapid processability> Similar to the evaluation of sensitometry, each sample was sandwiched between the fluorescent intensifying screens 1 and irradiated with X-rays SRX-50.
3 Modify the automatic processor so that the processing time is as follows
Processing was performed with an R-DF processing solution at a developing temperature of 35 ° C. The replenishment rate of the processing solution is 125 ml / m ^{2 for} both developer and fixer.
Processed.

Development time: 4 seconds Fixing time: 3.1 seconds Water washing time: 2 seconds Water washing-drying (squeeze): 1.6 seconds Drying time: 4.3 seconds Total processing time: 15 seconds Also with an automatic developing machine The running variation of the above was evaluated as follows. Using the above-mentioned automatic processor and the processing agent, after processing 200 sheets of a large-angle size (35.6 × 35.6 cm) sample exposed to light so that the density after development is about 1.0, Similarly, the sample irradiated with X-ray was processed.

<Evaluation of Graininess> For each fluorescent intensifying screen / photosensitive material combination whose sensitivity was evaluated, a chest phantom manufactured by Kyoto Kagaku Co., Ltd. was used with an X-ray source of 120 kVp (equipped with an aluminum equivalent filter of 3 mm thickness), and A phantom was placed at a position of 140 cm, an anti-scatter grid with a grid ratio of 8: 1 was placed behind it, and a light-sensitive material and a fluorescent intensifying screen were placed behind it to perform photography.

In each of the photographs, the X-ray exposure amount was adjusted by changing the exposure time so that the highest density portion of the lung field was 1.8 ± 0.5. The obtained photographs were visually observed, and the graininess was evaluated according to the following evaluation criteria.

Graininess Evaluation Criteria A: Almost inconspicuous B: Slightly conspicuous C: Conspicuous and some trouble in image interpretation D: Very conspicuous and trouble in image interpretation The above results are shown in Table 2.

[0168]

[Table 2]

From the results shown in Table 2, it can be seen that the sample of the present invention has excellent CP, good graininess, high sensitivity and low fog even by ultra-rapid processing.

Example 3 Treatment 2 (Development Treatment Using Solid Processing Agent Containing Hydroquinone) A developing (replenishing) tablet was prepared according to the following procedure (A, B). The development and the replenishment are the same.

Operation (A) 3000 g of hydroquinone as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm. 3000 g of sodium sulfite and 2 parts of potassium sulfite were added to the fine powder.
000 g and 1000 g of dimezone S (1-phenyl-4-hydroxymethyl-4-methylpyrazolidone) were added,
After mixing in a mill for 30 minutes and granulating in a commercial stirred granulator at room temperature for about 10 minutes by adding 30 ml of water, the granulate is dried in a fluid bed dryer at 40 ° C. for 2 minutes. The granules are dried for an hour to almost completely remove water. In this way, polyethylene glycol 600 is added to the prepared granules.
100 g of 0 was uniformly mixed for 10 minutes using a mixer in a room where the humidity was controlled to 25 ° C. and 40% RH or less, and the obtained mixture was tough pressed collect 1 manufactured by Kikusui Seisakusho KK
Using a tableting machine modified from 527HU, the filling amount per tablet was 3.84 g, and compression tableting was performed to prepare 2500 developing (supplementary) tablet A agents.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohyphoxanthine, 200 g of KOH, N-acetyl-D and L-penicillamine were operated. It grind | pulverizes and granulates like (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture obtained in this manner was compressed into tablets using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with the filling amount per tablet being 1.73 g, and subjected to compression tableting.
0 developing (supplementary) tablet B agents were prepared.

Next, a fixing (replenishing) tablet was prepared by the following procedure. The fixing and the fixing replenishing are the same.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
Granulate with l. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the granules thus prepared, and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the mixture thus obtained was compressed into tablets with a filling amount of 6.202 g per tablet using a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd. ) Tablet C agent was prepared.

Operation (D) 1000 g of boric acid, 150 aluminum sulfate and 18 hydrates
0 g, sodium hydrogen acetate (equimolar mixture of glacial acetic acid and sodium acetate and dried) 3000 g, tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and the mixture was mixed for 3 minutes, and then the obtained mixture was mixed with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compressed into tablets with a filling amount of 4.562 g and 1250 fixing (replenishing) tablets D
A preparation was made.

[0176]

At the start of processing of the developing solution (starting of running), 16.5 liters of a developing solution prepared by diluting 434 developing tablets A and B with diluting water were used, and a starter 3 was used.
The processing was started by filling the developing tank with the liquid to which 30 ml was added as a starting liquid. The pH of the developer to which the starter was added was 10.45.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For running, an automatic processor SRX-502 equipped with a solid processing agent charging member and modified so as to be processed at a processing speed of 15 seconds was used. During running, the developer was added to the developer at a rate of 0.62 m ² for each of the above ^two agents A and B and 76 ml of water (replenishing amount: 122.6 ml / m ² ). The pH of each of the agents A and B dissolved in 38 ml of water was 10.70. To the fixing solution were added ² parts of the above C agent, 1 part of the D agent and 74 ml of water (replenishment amount: 119.3 ml / m ² ) per 0.62 m ² of the light-sensitive material.
For each treatment agent, the rate of water addition started at about the same time as the addition of the treatment agent and was approximately proportional to the dissolution rate of the treatment agent.
Minutes at a constant speed.

Processing conditions Development time: 4 seconds Fixing time: 3.1 seconds Water washing time: 2 seconds Water washing-drying (squeeze): 1.6 seconds Drying time: 4.3 seconds Total processing time: 15 seconds Example 2 The same evaluation as the above was performed under the above processing conditions.

The results are shown in Table 3.

[0181]

[Table 3]

From the results shown in Table 3, it can be seen that the samples of the present invention have excellent CP, good graininess, high sensitivity and low fog even by ultra-rapid processing.

Example 4 Process 3 (Development Process Using Solid Processing Agent Not Containing Hydroquinone) A developing (replenishing) tablet containing no hydroquinone was prepared according to the following procedure (E, F).

Operation (E) 13,000 g of sodium erythorbate as a developing agent is ground in a commercial Van Dam mill until the average particle size becomes 10 μm. Sodium sulfite (4877 g), phenidone (975 g) and DTPA (1635 g) were added to this fine powder and the mixture was mixed in a mill for 3
After mixing for 0 minutes and granulating by adding 30 ml of water in a commercial stirred granulator at room temperature for about 10 minutes, the granulate is dried in a fluid bed dryer at 40 ° C. for 2 hours. To almost completely remove the water content of the granulated product. 2167 polyethylene glycol 6000 was added to the granulated product thus prepared.
g was uniformly mixed for 10 minutes using a mixer in a room where the humidity was adjusted to 25 ° C. and 40% RH or less, and the obtained mixture was toughly pressed collect 1527HU manufactured by Kikusui Seisakusho KK
With a tableting machine modified from the above, the filling amount per tablet was 8.71.
The tablets were made into 5 g and compressed into tablets to prepare 2500 developing (supplementary) tablet E agents.

Operation (F) Potassium carbonate 19,500 g, 1-phenyl-5-mercaptotetrazole 8.15 g, sodium hydrogencarbonate 3.
25 g, 650 g of glutaraldehyde sulfite adduct, and 1354 g of polyethylene glycol 6000 are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 30.0
ml, and after granulation, dried at 50 ° C. for 30 minutes to remove almost completely the moisture of the granulated material. The mixture obtained in this manner is used as a tough press collect 152 manufactured by Kikusui Seisakusho Co., Ltd.
Using a tableting machine modified from 7HU, the filling amount per tablet was set to 9.90 g, and compression tableting was performed to prepare 2500 developing (supplementing) tablet F agents.

Next, a fixing (replenishing) tablet was prepared by the following procedure.

Operation (G) 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide and 2.32 g of ethylenediaminetetraacetic acid disodium salt are pulverized and granulated in the same manner as in (A). The amount of water added was 500 ml, and after granulation,
The granulated product is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product. The thus-obtained mixture was loaded into a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 8.214 g.
Compressed and compressed into 2,500 pieces for fixing (replenishment)
Tablet G preparation was prepared.

Operation (H) 1860 g of boric acid, 650 aluminum sulfate sulfate 650
0 g, glacial acetic acid 1860 g, sulfuric acid (50 wt%) 928 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 1
The volume of the granules is adjusted to 00 ml, and after granulation, the granules are dried at 50 ° C. for 30 minutes to almost completely remove water. The mixture thus obtained was used as a tough pressed collect 1 by Kikusui Seisakusho KK
Using a tableting machine modified from 527HU, the amount of filling per tablet was 4.459 g, and compression tableting was performed to prepare 2500 fixing (replenishing) tablet H agents.

[0189]

At the start of processing of the developing solution (starting of running), 1650 liters of developing tablet E agent and 825 F agent were diluted with diluted water to prepare 16.5 liters of a developing solution, to which 330 ml of a starter was added. Processing was started by filling the developing tank as a start solution. The pH of the developer to which the starter was added was 10.45.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 equipped with a charging member of a solid processing agent and modified so as to be able to process at a processing speed of 25 seconds was used.

During running, the photosensitive material was 1.0 in the developer.
One E agent, two F agents and 20 m water per 0 m ^2.
1 (replenishing amount of 20 ml / m ² ) was added. Each E agent,
When the F agent was dissolved in 20 ml of water, the pH was 10.70.
Met. The fixing solution contains four G agents, two H agents and 50 ml of water per 1.00 m ² of the light-sensitive material (replenishment amount of 50 m
1 / m ² ) was added. The rate of water addition to each of the treatment agents was started almost at the same time as the addition of the treatment agent, and was added at a constant rate for 10 minutes in proportion to the dissolution rate of the treatment agent.

Processing conditions Development time: 4 seconds Fixing time: 3.1 seconds Water washing time: 2 seconds Water washing-drying (squeeze): 1.6 seconds Drying time: 4.3 seconds Total processing time: 15 seconds Example 2 The same evaluation as the above was performed under the above processing conditions.

The results are shown in Table 4.

[0195]

[Table 4]

From the results shown in Table 4 using the solid processing agent, it is understood that the sample of the present invention has excellent CP, good graininess, high sensitivity even by ultra-rapid processing, and low fog.

[0197]

The present invention provides a method for producing a silver halide emulsion having a narrow grain size distribution and a high tabular ratio, and
It was possible to provide a method for producing a silver halide emulsion having a low fog, a high sensitivity, and a high CP, which is extremely rapid and has excellent replenishment processability, a silver halide photographic light-sensitive material, and an X-ray image forming method.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/46 G03C 1/46 5/17 5/17 5/26 5/26 520 520 5/29 5/29 5/305 5/305 5/31 5/31 5/395 5/395 G21K 4/00 G21K 4/00 A

Claims (8)

[Claims] 1. The silver chloride content is 20 to 100 mol%, and 30 to 100% of the total projected area has two parallel main planes (100) planes and an aspect ratio of 2 to 50.
In the method for producing a silver halide emulsion which is a tabular grain, the production method includes a nucleation step, an Ostwald ripening step,
And a grain growth step, which does not substantially contain iodine at the time of nucleation of the grain, and an iodide is added between immediately after the nucleation of the grain and before the completion of the Ostwald ripening step. Method for producing silver emulsion. 2. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, wherein the silver halide emulsion according to claim 1 is contained in the emulsion layer. Silver halide photographic light-sensitive material. 3. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, wherein the silver halide grains contained in the emulsion layer have a silver chloride content of 20 to 100.
Mol%, 30 to 100% of the total projected area is two parallel main planes (100), and the aspect ratio is 2 to
A silver halide photographic light-sensitive material, which is 50 tabular grains and has a circular shape having a linear portion ratio of the main plane of the grains of 0 to 3/4. 4. The silver halide photographic light-sensitive material according to claim 2 or 3 is a double-sided light-sensitive material, and the light-sensitive material exhibits an absorption amount of 45 to 100% for X-rays having an X-ray energy of 80 kVp. An X-ray image characterized by performing imagewise exposure by irradiating X-rays with a fluorescent substance filling rate of 68 to 90% and a fluorescent substance having a thickness of 135 μm to 200 μm. Forming method. 5. A method for forming an image by irradiating an X-ray using the fluorescent intensifying screen and the silver halide photographic light-sensitive material according to claim 4, wherein the silver halide photographic light-sensitive material is placed in a processing tank. An X-ray image forming method comprising processing with an automatic processor having a mechanism for supplying a solid processing agent. 6. The X-ray image forming method according to claim 4, wherein the silver halide photographic light-sensitive material contains a developer and / or a development replenisher containing a compound represented by the following general formula (1). An X-ray image forming method, which comprises processing with an automatic processor using a liquid. Embedded image [In the formula, R ₁ and R ₂ each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. X represents an atomic group necessary to form a 5- or 6-membered ring with the two vinyl carbon atoms and the carbonyl carbon atom which are substituted by R ₁ and R ₂ . ] 7. X according to any one of claims 4 to 6.
In the line image forming method, the silver halide photographic light-sensitive material is processed with an automatic processor for a total processing time of 10 to 25 seconds, which is an X-ray image forming method. 8. The X-ray image forming method according to claim 7, wherein the replenishing amount of the developing solution and / or the fixing solution is 10 to 200 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. Forming method.